Process for alkyne hydrosilation using cycloalkenes as catalyst modifiers

ABSTRACT

An improved process for hydrosilating alkynes with organodihalosilanes and trihalosilanes in the presence of a platinum catalyst selected from a group consisting of platinum halides and reaction product of platinum halides with organosilicon compounds having terminal aliphatic unsaturation. The process uses a cycloalkene comprising about six to 20 carbon atoms as a catalyst modifier to reduce formation of the bis-silated adduct of the alkynes.

BACKGROUND OF INVENTION

The present invention is an improved process for hydrosilating alkynes with organodihalosilanes and trihalosilanes in the presence of a platinum catalyst selected from a group consisting of platinum halides and the reaction product of platinum halides with organosilicon compounds having terminal aliphatic unsaturation. The process uses a cycloalkene comprising about six to 20 carbon atoms as a catalyst modifier to reduce formation of the bis-silated adduct of the alkynes.

Virtually any compound which contains a ≡SiH group can be reacted with compounds containing aliphatic unsaturation in the presence of a platinum compound such as chloroplatinic acid to effect a reaction typically referred to as hydrosilation or hydrosilylation. Speier et al., U.S. Pat. No. 2,823,218, discuss such hydrosilation reactions in detail.

Willing, U.S. Pat. No. 3,419,593, describes a group of catalysts that are the reaction product of chloroplatinic acid with organosilicon compounds having terminal unsaturation that are particularly useful in many such hydrosilation processes.

Lindner et al., U.S. Pat. No. 4,292,434, describe a hydrosilation catalytic mixture obtained by dissolving a platinum halide in at least 20 parts by weight of olefin for each part by weight of platinum halide and subsequently heating and mixing the solution obtained with from 0.5 to one mole of a primary or secondary amine for each gram atom of platinum.

A common problem associated with the hydrosilation of an alkyne with a hydridosilane in the presence of a platinum halide or platinum olefin complex as catalyst is the formation of the bis-silated adduct of the alkyne as a by-product. Typically such hydrosilation processes are run under high pressure to increase the concentration of alkyne in the reaction mixture relative to the alkenyl substituted product thereby minimizing the formation of the bis-silated adduct of the alkyne. However alkynes such as acetylene are explosive at high pressures, thereby making such processes dangerous. The present inventors have discovered that in processes where an alkyne is silated with either a trihalosilane or organodihalosilane in the presence of a platinum catalyst selected from a group consisting of platinum halides and reaction product of platinum halide with organosilicon compounds having terminal aliphatic unsaturation, the presence of a cycloalkene comprising about six to 20 carbon atoms can reduce the amount formed of the bis-silated adduct of the alkyne. This reduction can allow such processes to be run at near normal atmospheric pressure while still providing for an acceptable ratio of alkenyl substituted product to bis-silated adduct of the alkyne.

SUMMARY OF INVENTION

The present invention is an improved process for hydrosilating alkynes with organodihalosilanes and trihalosilanes in the presence of a platinum catalyst selected from a group consisting of platinum halides and reaction product of platinum halides with organosilicon compounds having terminal aliphatic unsaturation. The process uses a cycloalkene comprising about six to 20 carbon atoms as a catalyst modifier to reduce formation of the bis-silated adduct of the alkynes.

DESCRIPTION OF INVENTION

The present invention is a process for hydrosilation of an alkyne. The process comprises: contacting at a temperature within a range of about 40° C. to 150° C. an alkyne described by formula

    R.sup.1 C≡CH,                                        (1)

where R¹ is selected from a group consisting of hydrogen atom and alkyls comprising one to ten carbon atoms; with a hydridosilane described by formula

    R.sup.2.sub.n HSiX.sub.3-n,                                (2)

where R² is selected from a group consisting of alkyls comprising one to 20 carbon atoms and aryls, each X is an independently selected halogen, and n has a value of zero or one; in the presence of a platinum catalyst selected from a group consisting of platinum halides and reaction product of platinum halides with organosilicon compounds having terminal aliphatic unsaturation and a cycloalkene comprising about six to 20 carbon atoms in an amount sufficient to reduce formation of a bis-hydrosilated adduct of the alkyne.

The alkyne can be contacted with the hydridosilane in standard low-pressure reactors suitable for reacting such compounds. The pressure at which the present process is conducted is not critical and can be varied within a wide range. However, the present process is advantageous in that it can be conducted at near-normal atmospheric pressure while still providing for an acceptable ratio of alkenyl-substituted product to bis-silated by-product. Therefore, it is preferred that the process be conducted at a pressure within a range of about 0.1 to 3 atmospheres. More preferred is when the process is conducted at a pressure within a range of about 1 to 3 atmospheres.

The present process can be conducted in either a gas or liquid phase. However, it is preferred that the process be conducted in a liquid phase using a liquid hydrocarbon solvent in which the alkyne and hydridosilane are soluble. It is preferred that the liquid hydrocarbon solvent having a boiling point greater than the boiling point of the alkenyl substituted product of the process to facilitate separation of the product from the solvent. The solvent can be, for example, an aromatic hydrocarbon such as xylene or a mixture of the isomers of xylene, toluene, or benzene. An example of such a liquid phase process is provided in the Examples herein.

The present process is conducted at a temperature within a range of about 40° C. to 150° C. A preferred temperature is within a range of about 60° C. to 100° C. The optimal temperature for conducting the process will depend upon such factors as the alkyne and hydridosilane to be reacted. For example, when acetylene is reacted with methyldichlorosilane a preferred temperature for conducting the process is within a range of about 70° C. to 80° C.

Alkynes useful in the present process are described by formula (1), where R¹ is selected from a group consisting of hydrogen atoms and alkyls comprising one to ten carbon atoms. R¹ can be, for example, methyl, ethyl, propyl, tert-butyl, and decyl. Preferred is when R¹ is hydrogen, making the alkyne acetylene.

Hydridosilanes useful in the present process are described by formula (2), where R² is selected from a group consisting of alkyls comprising one to 20 carbon atoms and aryls, each X is an independently selected halogen, and n has a value of zero or one. R² can be, for example, alkyls such as methyl, ethyl, propyl, and tert-butyl; halogen substituted alkyls such as chloromethyl and 3,3,3-trifluoropropyl; aryls such as phenyl, tolyl, and xylyl; and halogen substituted aryls such as chlorophenyl. Preferred is when R² is methyl. Preferred is when X is a chlorine atom. The preferred hydridosilane is selected from a group consisting of trichlorosilane and methyldichlorosilane. The most preferred hydridosilane is methyldichlorosilane.

In the present process it is preferred that the mole ratio of the alkyne to the hydridosilane fed to the process be within a range of about 0.5:1 to 3:1. Preferred is when the mole ratio of alkyne to hydridosilane is within a range of about 1:1 to 1.3:1.

The present process is conducted in the presence of a platinum catalyst selected from a group consisting of platinum halides and reaction product of platinum halides with organosilicon compounds having terminal aliphatic unsaturation. Platinum halides useful in the present invention include platinum dichloride, platinum dibromide, platinum tetrachloride, dipotassium tetrachloroplatinate (i.e. K₂ PtCl₄), and chloroplatinic acid (i.e. H₂ PtCl₆.6H₂ O). The preferred platinum halide is chloroplatinic acid. Platinum catalysts useful in the present invention also include the reaction product of a platinum halide with an organosilicon compound having terminal aliphatic unsaturation. Such catalysts are described, for example, in Willing, U.S. Pat. No. 3,419,593, which is incorporated by reference for its teaching of platinum catalysts useful in the present process. A preferred catalyst for use in the present process is the reaction product of a solution of chloroplatinic acid in 2-propanol with methylvinyldichlorosilane as described in the examples herein. Other preferred catalysts for use in the present process include the reaction products of platinum dichloride or chloroplatinic acid with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

The concentration of platinum catalyst used in the present process can be varied within wide limits. In general, when the process is run as a batch process in the liquid phase the catalyst concentration in the liquid phase can be that providing about one to 20,000 ppm platinum. Preferred is when the catalyst provides about 100 to 10,000 ppm platinum in the liquid phase.

The present process requires the presence of a cycloalkene comprising about six to 20 carbon atoms in an amount sufficient to reduce the formation of a bis-hydrosilated adduct of the alkyne. Preferred are those cycloalkenes which do not undergo hydrosilation under process conditions to create unwanted by-products. Preferred is when the cycloalkene comprises about seven to 10 carbon atoms. The cycloalkene can be, for example, cyclohexene, cycloheptene, cyclooctene, cyclodecene and norborene. The preferred cycloalkene is cyclooctene. In general an amount of cycloalkene sufficient to reduce the formation of a bis-hydrosilated adduct of the alkyne is about 200 to 5,000 moles cycloalkene per each g•atom of platinum provided by the platinum catalyst to the process. Preferred is when the ratio of moles cycloalkene to g•atom platinum is within a range of about 500:1 to 3,500:1.

Another benefit of the present process is that the addition of the cycloalkene improves the solubility of the platinum catalyst in the process allowing for more efficient use of the platinum catalyst.

The following examples are provided to illustrate the present invention. These examples are not intended to limit the scope of the claims herein.

The platinum catalysts used in the examples are as follows. The catalyst designated as "CPA/IPA/MeViSiCl₂ " was prepared by the following method. A 500 mL, round-bottom flask, equipped with a stirring bar was flushed with nitrogen and charged with 296.2 g of distilled methylvinyldichlorosilane. 3.77 g of a solution comprising chloroplatinic acid in 2-propanol and containing 4.39 percent by weight platinum, obtained from Johnson-Matthey, Ward Hill, Mass., was slowly added to the flask. This mixture was stirred for about 15 hours under nitrogen and then transferred to a clean, stoppered glass bottle for storage. A similar catalyst solution containing one-fourth the concentration of platinum metal was also prepared and used in some of the examples. However, in all examples the final concentration of platinum was the same.

The catalyst designated as "CPA/IPA/Me₂ ViSiCl" was prepared by adding 2.51 g of the solution comprising chloroplatinic acid in 2-propanol, as described above, to 197.5 g of distilled Me₂ ViSiCl. The resulting mixture was treated by a method similar to that described for preparing the CPA/IPA/MeViSiCl₂ catalyst.

The catalyst designated as "Pt/Vinyldisiloxane Complex" is a solution of a complex of chloroplatinic acid and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane prepared by a method similar to that described in Willing, U.S. Pat. No. 3,419,593.

The apparatus set-up for running the examples is as follows. Commercially acquired acetylene was purified to remove stabilizing agents. The purified acetylene was introduced via a coarse glass-frit gas dispersion tube into a 500 mL, 3-neck, round-bottom flask containing liquid hydridosilane. This flask, termed the "SiH reservoir", was fitted with a thermometer and equipped with teflon adapters at the necks for entry of delivery and exit tubes. The exit tube from the SiH reservoir was a 6 mm O.D. polypropylene tube leading to a 500 mL flask used as a safety trap between the SiH reservoir and the reaction flask. The tubing exiting the safety trap was a 3 mm O.D. teflon tube. This exit tube was connected to a second gas dispersion tube which entered a 1 L, 3-neck, round-bottom flask termed the "reactor". The reactor was equipped with a stirring bar and fitted with a thermometer at one neck and a claisen adapter on the center neck. The straight neck of the claisen adaptor was equipped with a rubber septum for the periodic withdrawal of samples from the reactor for analysis by gas chromatography using a thermal conductivity detector (GC-TCD). The second neck of the claisen adapter was fitted with a dewar condenser cooled with a dry ice/isopropyl alcohol (IPA) bath. The tygon tubing exiting this condenser led to a mineral oil double-bubbler via a dry ice/IPA trap. Provisions were made for blanketing and or purging the apparatus from just before the SiH reservoir to between the last dry ice/IPA trap and the bubbler.

The experimental procedure for running the examples is as follows. Hydridosilane was added to the SiH reservoir, which was maintained at a constant temperature of about 18° C. when the hydridosilane was methyldichlorosilane and about 13° C. when the hydridosilane was dimethylchlorosilane. A preweighed quantity of catalyst and catalyst modifier was added to the reactor. Based on approximately one g-mol of product formed during a run, the amount of catalyst used provided a final Pt/SiH mole ratio of about 6×10⁻⁵ :1 in each example. Methylvinyldichlorosilane or dimethylvinylchlorosilane (as a means of varying the average amount of vinylsilane concentration in the reactor) and xylenes in the amounts described in each example were transferred to the reactor under a slow nitrogen purge.

The reaction apparatus was purged with acetylene and then the gas dispersion tube in the SiH reservoir was slowly lowered into the hydridosilane so as to bubble acetylene through the hydridosilane. The acetylene flow rate was maintained at about 115 to 120 mL minute so as to yield approximately 120 to 170 g of vinylsilane product in a three to four hour run time. The gas exiting the SiH reservoir comprised acetylene and hydridosilane at a molar ratio within a range of 1.2:1 to 1.25:1. The gaseous mixture was passed into the stirring catalyst solution in the reactor. Within one to three minutes, an exotherm was evident. The temperature of the reactor was controlled by means of a silicone oil bath to maintain the temperatures reported for each example. The exotherm usually reached a peak in 30 to 45 minutes. The reaction temperature was then maintained at a constant temperature as reported for each example for the remainder of the run. When the level of liquid in the reactor reached a preset mark on the flask corresponding to the approximate product weight as described in each example, the gas dispersion tube in the SiH reservoir was raised above the liquid level to stop any further hydrosilation. Acetylene flow was continued for 2 to 5 minutes longer. The reactor was cooled to room temperature under nitrogen atmosphere and the product mixture was removed under nitrogen pressure into a preweighed bottle.

The weight of all products formed was obtained by subtracting the weight of the initial reaction mixture (i.e. catalyst, catalyst modifier, vinylsilane, and xylenes) from that of the final product mixture. Analysis of the mixture was performed by GC-TCD.

In the examples the following labels apply. "Catalyst" is the type catalyst used, as previously described; "Catalyst Conc." is the initial g•atoms of platinum per mole of SiH added to the reactor; "Catalyst Modifier" is the type and weight of unsaturated cyclic compound added to the reactor to attempt suppression of the bis-silated adduct of acetylene; "Additional MeViSiCl₂ " and "Additional Me₂ ViSiCl" is the weight of methylvinyldichlorosilane or dimethylvinylchlorosilane added to the reactor to vary the average concentration of vinylsilane in the reactor; "Xylenes" is the amount of a mixture of xylene isomers added to the reactor; "Temperature Range" describes the temperature range of the reactor that occurred from initiation of the exotherm to temperature stabilization; "Hold Temp." is the constant temperature the content of the reactor was held at after temperature stabilization. "Average MeViSiCl₂ Conc." and "Average Me₂ ViSiCl" is the average concentration by weight of these compounds in the reactor during a run; "Weight MeViSiCl₂ " and "Weight Me₂ ViSiCl" is the weights of methylvinyldichlorosilane or dimethylvinylchlorosilane made by the process, as determined by GC-TCD and corrected for any such compound initially added to the reactor; "Weight Bis-Silated Derivative" is the amount of the bis-silated acetylene made during conduct of the process; "P/B weight Ratio" is the weight ratio of product MeViSiCl₂ or Me₂ ViSiCl to bis-silated acetylene adduct.

    ______________________________________                                         Example 1. (Reference Example)                                                 Catalyst          CPA/IPA/MeViSiCl.sub.2                                       Catalyst Conc.    6 × 10.sup.-5 g · atom Pt/mole SiH            Catalyst Modifier none                                                         Additional MeViSiCl.sub.2                                                                        135.2 g                                                      Xylenes            86.0 g                                                      Temperature Range  70-74° C.                                            Hold Temperature   71° C.                                               Average MeViSiCl.sub.2 Conc.                                                                      74 Wt. %                                                    Weight Product MeViSiCl.sub.2                                                                     99.1                                                        Weight Bis-Silated Derivative                                                                     12.9 g                                                      P/B Weight Ratio   7.7:1                                                       Example 2.                                                                     Catalyst          CPA/IPA/MeViSiCl.sub.2                                       Catalyst Conc.    6 × 10.sup.-5 g · atom Pt/mole SiH            Catalyst Modifier  6.4 g Cyclooctene                                           Additional MeViSiCl.sub.2                                                                        135.3 g                                                      Xylenes            81.7 g                                                      Temperature Range  69-78.5° C.                                          Hold Temperature   74° C.                                               Average MeViSiCl.sub.2 Conc.                                                                      76 Wt. %                                                    Weight Product MeViSiCl.sub.2                                                                    155.2 g                                                      Weight Bis-Silated Derivative                                                                     7.9 g                                                       P/B Weight Ratio   19.8:1                                                      Example 3.                                                                     Catalyst          CPA/IPA/MeViSiCl.sub.2                                       Catalyst Conc.    6 × 10.sup.-5 g · atom Pt/mole SiH            Catalyst Modifier  25.4 g Cyclooctene                                          Additional MeViSiCl.sub.2                                                                        200.0 g                                                      Xylenes            64.5 g                                                      Temperature Range  69-79° C.                                            Hold Temperature   75° C.                                               Average MeViSiCl.sub.2 Conc.                                                                      76 Wt. %                                                    Weight Product MeViSiCl.sub.2                                                                    155.1 g                                                      Weight Bis-Silated Derivative                                                                     4.5 g                                                       P/B Weight Ratio   34.8:1                                                      Example 4. (Reference Example)                                                 Catalyst          CPA/IPA/MeViSiCl.sub.2                                       Catalyst Conc.    6 × 10.sup.-3 g · atom Pt/mole SiH            Catalyst Modifier None                                                         Additional MeViSiCl.sub.2                                                                        127.3 g                                                      Xylenes           148.0 g                                                      Temperature Range  68.5-79° C.                                          Hold Temperature   77° C.                                               Average MeViSiCl.sub.2 Conc.                                                                      58 Wt. %                                                    Weight Product MeViSiCl.sub.2                                                                    164.7 g                                                      Weight Bis-Silated Derivative                                                                     10.7 g                                                      P/B Weight Ratio   15.4:1                                                      Example 5.                                                                     Catalyst          CPA/IPA/MeViSiCl.sub.2                                       Catalyst Conc.    6 × 10.sup.-5 g · atom Pt/mole SiH            Catalyst Modifier  5.9 g Cyclooctene                                           Additional MeViSiCl.sub.2                                                                        125.0 g                                                      Xylenes           144.0 g                                                      Temperature Range  70-80° C.                                            Hold Temperature   76° C.                                               Average MeViSiCl.sub.2 Conc.                                                                      58 Wt. %                                                    Weight Product MeViSiCl.sub.2                                                                    161.1 g                                                      Weight Bis-Silated Derivative                                                                     6.3 g                                                       P/B Weight Ratio   25.5:1                                                      Example 6.                                                                     Catalyst          Pt/Vinyldisiloxane Complex                                   Catalyst Conc.    6 × 10.sup.-5 g · atom Pt/mole SiH            Catalyst Modifier  11.9 g Cyclooctene                                          Additional MeViSiCl.sub.2                                                                        144.4 g                                                      Xylenes           138.0 g                                                      Temperature Range  70-81° C.                                            Hold Temperature   76° C.                                               Average MeViSMeViSiCl.sub.2 Conc.                                                                 57 Wt. \%                                                   Weight Product MeViSiCl.sub.2                                                                    167.4 g                                                      Weight Bis-Silated Derivative                                                                     6.4 g                                                       P/B Weight Ratio   26:1                                                        Example 7. (Reference Example)                                                 Catalyst          CPA/IPA/Me.sub.2 ViSiCl                                      Catalyst Conc.    6 × 10.sup.-5 ] atom Pt/mole SiH                       Catalyst Modifier None                                                         Additional Me.sub.2 ViSiCl                                                                       125.2 g                                                      Xylenes           150.0 g                                                      Temperature Range  69.5-79° C.                                          Hold Temperature   77° C.                                               Average Me.sub.2 ViSiCl Conc.                                                                     54 Wt. %                                                    Weight Product Me.sub.2 ViSiCl                                                                   102.6 g                                                      Weight Bis-Silated Derivative                                                                     17.1 g                                                      P/B Weight Ratio   6:1                                                         Example 8. (Reference Example)                                                 Catalyst          CPA/IPA/Me.sub.2 ViSiCi                                      Catalyst Conc.    6 × 10.sup.-5 g · atom Pt/mole SiH            Catalyst Modifier  5.9 g Cyclooctene                                           Additional Me.sub.2 ViSiCl                                                                       124.7 g                                                      Xylenes           144.0 g                                                      Temperature Range  69-79° C.                                            Hold Temperature   77° C.                                               Average Me.sub.2 ViSiCl Conc.                                                                     55 Wt. %                                                    Weight Product Me.sub.2 ViSiCl                                                                   106.2 g                                                      Weight Bis-Silated Derivative                                                                     16.8 g                                                      P/B Weight Ratio   6.3:1                                                       ______________________________________                                     

I claim:
 1. A process for hydrosilation of an alkyne, the process comprising:contacting at a temperature within a range of about 40° C. to 150° C. an alkyne described by formula

    R.sup.1 C≡CH,

where R¹ is selected from a group consisting of hydrogen atom and alkyls comprising one to ten carbon atoms; with a hydridosilane described by formula

    (R.sup.2).sub.n HSiX.sub.3-n,

where R² is selected from a group consisting of alkyls comprising one to 20 carbon atoms and aryls, each X is an independently selected halogen, and n has a value of zero or one; in the presence of a platinum catalyst selected from a group consisting of platinum halides and reaction product of platinum halides with organosilicon compounds having terminal aliphatic unsaturation and a cycloalkene comprising about six to 20 carbon atoms in an amount sufficient to reduce the formation of a bis-hydrosilated adduct of the alkyne.
 2. A process according to claim 1, where the contacting is conducted at a pressure within a range of about 0.1 to 3 atmospheres.
 3. A process according to claim 1, where the contacting is conducted at a pressure within a range of about 1 to 3 atmospheres.
 4. A process according to claim 1, where the contacting is conducted in a liquid phase using a liquid hydrocarbon solvent in which the alkyne and hydridosilane are soluble.
 5. A process according to claim 1, where the temperature is within a range of about 60° C. to 100° C.
 6. A process according to claim 1, where the hydridosilane is selected from a group consisting of trichlorosilane and methyldichlorosilane.
 7. A process according to claim 1, where the hydridosilane is methyldichlorosilane.
 8. A process according to claim 1, where the alkyne is acetylene, the hydridosilane is methyldichlorosilane and the temperature is within a range of about 70° C. to 80° C.
 9. A process according to claim 1, where the mole ratio of the alkyne contacted with the hydridosilane is within a range of about 0.1:1 to 3:1.
 10. A process according to claim 1, where the mole ratio of the alkyne to the hydridosilane fed to the process is within a range of about 1:1 to 1.3:1.
 11. A process according to claim 1, where the platinum catalyst is selected from a group consisting of chloroplatinic acid, reaction product of chloroplatinic acid with methylvinyldichlorosilane, reaction product of chloroplatinic acid with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and reaction product of platinum dichloride with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.
 12. A process according to claim 4 comprising about one to 20,000 ppm platinum in the liquid phase.
 13. A process according to claim 4 where the liquid phase comprises about 100 to 10,000 ppm platinum.
 14. A process according to claim 1 where the cycloalkene comprises about 7 to 10 carbon atoms.
 15. A process according to claim 1 where the cycloalkene is cyclooctene.
 16. A process according to claim 1 where the contacting is conducted in the presence of about 200 to 5,000 moles of cycloalkene per each g•atom of platinum provided by the platinum catalyst.
 17. A process according to claim 1 where the contacting is conducted in the presence of about 500 to 3,500 moles of cycloalkene per each g•atom of platinum provided by the platinum catalyst.
 18. A process according to claim 4, where the alkyne is acetylene, the hydridosilane is methyldichlorosilane, the cycloalkene is cyclooctene, where the contacting is conducted in the presence of about 500 to 3,500 moles of the cyclooctene per each g•atom of platinum provided by the platinum catalyst, and the temperature is within a range of about 70° C. to 80° C. 